Sunscreen compositions having synergistic combination of uv filters

ABSTRACT

The disclosure relates to sunscreen compositions having a synergistic combination of ultraviolet light (UV) filtering agents that provide a high sun protection factor (SPF). Compositions according to the disclosure have high SPF values without requiring high overall amounts of UV filtering agents, and without requiring the use of oxybenzone. Furthermore, the disclosure relates to methods of using the described compositions for protecting keratinous substances such as skin and hair from UV radiation.

FIELD OF THE DISCLOSURE

The present disclosure relates to sunscreen compositions comprising asynergistic combination of ultra violet (“UV”) filters, and to methodsof using the combination of UV filters to protect keratinous substratessuch as skin and hair from UV radiation.

BACKGROUND

The negative effects of exposure to ultraviolet (“UV”) light arewell-known. Prolonged exposure to sunlight causes damage such as sunburnto the skin and dries out hair making it brittle. When skin is exposedto UV light having a wavelength of from about 290 nm to about 400 nm,long term damage can lead to serious conditions such as skin cancer.

UV light also contributes to aging by causing free radicals to form inthe skin. Free radicals include, for example, singlet oxygen, hydroxylradical, the superoxide anion, nitric oxide and hydrogen radicals. Freeradicals attack DNA, membrane lipids and proteins, generating carbonradicals. These in turn react with oxygen to produce a peroxyl radicalthat can attack adjacent fatty acids to generate new carbon radicals.This cascade leads to a chain reaction producing lipid peroxidationproducts. Damage to the cell membrane results in loss of cellpermeability, increased intercellular ionic concentration, and decreasedability to excrete or detoxify waste products. The end result is a lossof skin elasticity and the appearance of wrinkles. This process iscommonly referred to as photo-aging.

Sunscreens can be used to protect against UV damage and delay the signsof aging. The degree of UV protection afforded by a sunscreencomposition is directly related to the amount and type of UV filterscontained therein. The higher the amount of UV filters, the greater thedegree of UV protection. Nevertheless, it is desirable to achieve thebest photo protection efficacy with the lowest amount of UV filters. Theinventors of the instant disclosure discovered ways to attain SPFs thatwere not previously attainable with such low amounts of overall UVfilters.

SUMMARY OF THE INVENTION

The present disclosure relates to sunscreen compositions that have lowamounts of UV filters, require very little or no oxybenzone, and haveexcellent Sun Protection Factors (SPF). Typically, the higher amount ofUV filters (in particular oxybenzone) in a sunscreen composition thehigher the SPF. The inventors discovered, however, that whenoctocrylene, avobenzone, octyslate, and homosalate (UV filters) arecombined in particular ratios, they interact synergistically to exhibita surprisingly effective SPF. This allows for the elimination of most orall oxybenzone and a low overall amount of other UV filters.

The present disclosure also relates to a sunscreen composition havingthe following combination of UV filters: octocrylene, avobenzone,octyslate, and homosalate, and optionally oxybenzone; wherein the ratioof each filter relative to avobenzone is as follows:

the ratio of octocrylene to avobenzone is 1.6:1.0 to 2.4:1.0;

the ratio of oxybenzone to avobenzone 0.0:1.0 to 0.016:1.0;

the ratio of octyslate to avobenzone is 1.3:1.0 to 2.0:1.0; and

the ratio of homosalate to avobenzone is 2.3:1.0 to 3.6:1.0.

In particular the ratio of the ratio of each filter relative toavobenzone is about: 2.0:1.0:0.0:1.7:3.0(octocrylene:avobenzone:oxybenzone:octyslate:homosalate).

In one embodiment the UV filters are present in the followingpercentages by weight relative to the entire weight of the sunscreencomposition:

2 to 7 wt. % octocrylene;

1 to 3 wt. % avobenzone;

1 to 5 wt. % octisalate; and

2 to 10 wt % homosalate.

In another embodiment the UV filters are present in the followingpercentages by weight relative to the entire weight of the sunscreencomposition: about 5.9 wt. % octocrylene; about 3.0 wt. % avobenzone;about 4.9 wt. % octysalate; and about 8.8 wt. % homosalate. Typically,the sunscreen compositions are free of oxybenzone, or have less than1.0, 0.5, 0.25, or 0.05 wt. % oxybenzone.

The present disclosure is also directed to methods of protecting akeratinous substrate from ultraviolet radiation and to methods ofabsorbing ultraviolet light. Such methods encompass applying a sunscreencomposition to a keratinous substrate and subjecting the keratinoussubstrate to ultraviolet radiation.

DETAILED DESCRIPTION

The present disclosure also relates to a sunscreen composition havingthe following combination of UV filters: octocrylene, avobenzone,octyslate, and homosalate, and optionally oxybenzone; wherein the ratioof each filter relative to avobenzone is as follows:

the ratio of octocrylene to avobenzone is 1.6:1.0 to 2.4:1.0;

the ratio of oxybenzone to avobenzone 0.0:1.0 to 0.016:1.0;

the ratio of octyslate to avobenzone is 1.3:1.0 to 2.0:1.0; and

the ratio of homosalate to avobenzone is 2.3:1.0 to 3.6:1.

Typically, the sunscreen compositions are free of oxybenzone, or haveless than 0.025, 0.05, 0.10, 0.50 or 1.00 wt. % oxybenzone.

In particular the ratio of each filter relative to avobenzone is about:2.0:1.0:0.0:1.7:3.0(octocrylene:avobenzone:oxybenzone:octyslate:homosalate).

In one embodiment the UV filters are present in the followingpercentages by weight relative to the entire weight of the sunscreencomposition:

-   -   from 1, 2, 3, 4, or 5 to 5, 6, 7, 8, 9 or 10 wt. % octocrylene    -   from 1, 2, or 3 to 3, 4, or 5 wt. % avobenzone;    -   from 1, 2, 3, 4, or 5 to 5 wt. % octisalate; and    -   from 1, 2, 4, 6, 8, or 10 to 10, 12, 14, 15 wt. % homosalate.

In another embodiment the UV filters are present in the followingpercentages by weight relative to the entire weight of the sunscreencomposition: about 5.9 wt. % octocrylene; about 3.0 wt. % avobenzone;about 4.9 wt. % octysalate; and about 8.8 wt. % homosalate.

The present disclosure makes it possible to achieve the described SPFsin sunscreen compositions without the use of boosters, or essentiallywithout the use of boosters, e.g., sorbeth-2-hexaoleate. Althoughboosters may be included in the sunscreen compositions of the instantdisclosure, they are not required.

The present disclosure is also directed to methods of protecting akeratinous substrate from ultraviolet radiation and to methods ofabsorbing ultraviolet light. Such methods encompass applying a sunscreencomposition to a keratinous substrate and subjecting the keratinoussubstrate to ultraviolet radiation.

Where the following terms are used in this specification, they are usedas defined below.

The terms “comprising,” “having,” and “including” are used in theiropen, non-limiting sense.

The terms “a” and “the” are understood to encompass the plural as wellas the singular.

As used herein, the expression “at least one” means one or more and thusincludes individual components as well as mixtures/combinations.

“Cosmetically acceptable” means that the item in question is compatiblewith any keratinous substrate. For example, “cosmetically acceptablecarrier” means a carrier that is compatible with any keratinoussubstrate.

A “physiologically acceptable medium” means a medium which is not toxicand can be applied to the skin, lips, hair, scalp, lashes, brows, nailsor any other cutaneous region of the body. The composition of theinstant disclosure may especially constitute a cosmetic ordermatological composition.

The phrase “essentially without” refers to less than or equal to 0.5,0.1, 0.05 or 0.01 wt. %.

The phrase “stable emulsion” refers to a composition that does notundergo phase separation up to a temperature of 45 C.°.

Oils/Emollients

Examples of oils/emollients that may be included in the sunscreencompositions include: hydrocarbon-based oils of plant origin, such asliquid triglycerides of fatty acids containing from 4 to 10 carbonatoms, for instance heptanoic or octanoic acid triglycerides, oralternatively, for example, sunflower oil, corn oil, soybean oil, marrowoil, grapeseed oil, sesameseed oil, hazelnut oil, apricot oil, macadamiaoil, arara oil, coriander oil, castor oil, avocado oil, caprylic/capricacid triglycerides, for instance those sold by the company StearineriesDubois or those sold under the names Miglyol 810, 812 and 818 by thecompany Dynamit Nobel, jojoba oil, shea butter oil and caprylyl glycol;synthetic esters and ethers, especially of fatty acids, for instancePurcellin oil, 2-octyldodecyl stearate, 2-octyldodecyl erucate,isostearyl isostearate; hydroxylated esters, for instance isostearyllactate, octyl hydroxystearate, octyldodecyl hydroxystearate,diisostearyl malate or triisocetyl citrate; fatty alcohol heptanoates,octanoates or decanoates; polyol esters, for instance propylene glycoldioctanoate, neopentyl glycol diheptanoate and diethylene glycoldiisononanoate; and pentaerythritol esters, for instance pentaerythrityltetraisostearate, or isopropyl lauroyl sarcosinate, sold especiallyunder the trade name Eldew SL 205 by the company Ajinomoto; linear orbranched hydrocarbons, of mineral or synthetic origin, such as volatileor non-volatile liquid paraffins, and derivatives thereof, petroleumjelly, polydecenes, isohexadecane, isododecane, hydrogenatedpolyisobutene such as Parleam oil, or the mixture of n-undecane (C₁₁)and of n-tridecane (C₁₃) sold under the reference Cetiol UT by thecompany Cognis; fluoro oils that are partially hydrocarbon-based and/orsilicone-based, for instance those described in document JP-A-2 295 912;silicone oils, for instance volatile or non-volatile polymethylsiloxanes(PDMS) with a linear or cyclic silicone chain, which are liquid or pastyat room temperature, in particular volatile silicone oils, especiallycyclopolydimethylsiloxanes (cyclomethicones) such ascyclohexadimethylsiloxane and cyclopentadimethylsiloxane;polydimethylsiloxanes comprising alkyl, alkoxy or phenyl groups, whichare pendent or at the end of a silicone chain, these groups containingfrom 2 to 24 carbon atoms; phenyl silicones, for instance phenyltrimethicones, phenyl dimethicones,phenyltrimethylsiloxydiphenylsiloxanes, diphenyl dimethicones,diphenylmethyldiphenyltrisiloxanes or 2-phenylethyl trimethylsiloxysilicates, and polymethylphenylsiloxanes; mixtures thereof.

Additional examples include benzoic acid esters of C₉-C₁₅ alcohols,isononyl iso-nonanoate, C₁₂-C₁₅ alkyl benzoate, or any combinationsthereof.

Specific examples of oils/emollients include cocoglyceride,cyclomethicone, dimethicone, dicapryl maleate, caprylic/caprictriglyceride, isopropyl myristate, octyl stearate, isostearyl linoleate,lanolin oil, coconut oil, cocoa butter, olive oil, avocado oil, aloeextracts, jojoba oil, castor oil, fatty acid, oleic acid, stearic acid,fatty alcohol, cetyl alcohol, hexadecyl alcohol, diisopropyl adipate,hydroxybenzoate esters, benzoic acid esters of C₉-C₁₅ alcohols, isononyliso-nonanoate, alkanes, mineral oil, silicone, dimethyl polysiloxane,ether, polyoxypropylene butyl ether, polyoxypropylene cetyl ether,C₁₂-C₁₅ alkyl benzoate, aryl alkyl benzoate, Isopropyl Lauroylsarcosinate, and any combinations thereof.

Examples of hydrophilic organic solvents that may be included in thesunscreen compositions include:

-   -   monohydric C₁-C₈ alcohols such as ethanol, propanol, butanol,        isopropanol, isobutanol;    -   Polyethylene glycols from 6 to 80 ethylene oxides such as        propylene glycol, isoprene glycol, butylene glycol, glycerol,        sorbitol; mono or di-alkyl isosorbides such as dimethyl        isosorbide;

Examples of amphiphilic organic solvents include: polypropylene glycol(PPG) like propylene glycol alkyl ester or alkyl ether of PPG likePPG-23 oleyl ether and PPG-36 oleate.

The above lists are only examples and not limiting.

The total amount of oils/emollient present in the compositions istypically about 0.1, 0.5, 1.0, or 2.5 wt. % to about 5.0, 7.5, 10.0,15.0, 20.0, or 30 wt. % of the total weight of the composition.

Film Formers

Film-formers are often incorporated into sunscreen compositions toensure even coverage of the UV filters and can be used to render thecomposition water resistant. The film former is typically a hydrophobicmaterial that imparts film forming and/or waterproofing characteristics.One such agent is polyethylene, which is available from New PhaseTechnologies as Performalene® 400, a polyethylene having a molecularweight of 400. Another suitable film former is polyethylene 2000(molecular weight of 2000), which is available from New PhaseTechnologies as Performalene®. Yet, another suitable film former issynthetic wax, also available from New Phase Technologies as Performa®V-825. Other typical film-formers include acrylates/acrylamidecopolymer, acrylates copolymer, acrylates/C₁₂-C₂₂ alkylmethacrylatecopolymer, polyethylene, waxes,VP/dimethiconylacrylate/polycarbamylpolyglycol ester, butylated PVP,PVP/hexadecene copolymer, octadecene/MA copolymer, PVP/eicosenecopolymer, tricontanyl PVP, Brassica Campestris/Aleuritis Fordi Oilcopolymer, decamethyl cyclopentasiloxane (and) trimethylsiloxysilicate,and mixtures thereof. In some cases, the film former isacrylates/C₁₂-C₂₂ alkylmethacrylate copolymer sold under the tradenameAllianz OPT® by ISP.

Many of the common film-forming polymers included in sunscreencompositions are not soluble in ethanol (such as PVP/Eicosenecopolymer). A common film-former employed in ethanol based sunscreenproducts is Dermacryl LT or Dermacryl 79 marketed by Akzo Nobel (INCIName: acrylates/octylacrylamide copolymner). Dermacryl LT (CAS Number:80570-62-3) is a hydrophobic, high molecular weight carboxylated acryliccopolymer. It functions as a film-former in a broad range of cosmeticformulations, imparting waterproofing, increased occlusivity anddecreased rub-off of actives.

The above lists are only examples and not limiting.

The total amount of film-formers present in the compositions istypically in an amount of about 0.1, 0.5, 1.0, or 5 wt. % to about 5,10, 20, or 25 wt. %, based on the total weight of the composition.

Emulsifiers

The sunscreen compositions typically include at least one emulsifiersuch as an amphoteric, anionic, cationic or nonionic emulsifier, usedalone or as a mixture, and optionally a co-emulsifier. The emulsifiersare chosen in an appropriate manner according to the emulsion to beobtained (W/O or O/W). The emulsifier and the co-emulsifier aregenerally present in the composition in a proportion ranging from 0.3wt. % to 30 M. % and preferably from 0.5 wt. % to 20 wt. % by relativeto the total weight of the composition.

For W/O emulsions, examples of emulsifiers that may be mentioned includedimethicone copolyols, such as the mixture of cyclomethicone anddimethicone copolyol sold under the trade name DC 5225 C by the companyDow Corning, and alkyl dimethicone copolyols such as the lauryldimethicone copolyol sold under the name Dow Corning 5200 FormulationAid by the company Dow Corning, and the cetyl dimethicone copolyol soldunder the name Abil EM 90™ by the company Goldschmidt. A crosslinkedelastomeric solid organopolysiloxane comprising at least one oxyalkylenegroup, such as those obtained according to the procedure of Examples 3,4 and 8 of U.S. Pat. No. 5,412,004 and of the examples of U.S. Pat. No.5,811,487, especially the product of Example 3 (synthesis example) ofU.S. Pat. No. 5,412,004, such as the product sold under the referenceKSG 21 by the company Shin-Etsu, may also be used as surfactants for W/Oemulsions.

For O/W emulsions, examples of emulsifiers that may be mentioned includenonionic emulsifiers such as oxyalkylenated (more particularlypolyoxyethylenated) fatty acid esters of glycerol; oxyalkylenated fattyacid esters of sorbitan; oxyalkylenated (oxyethylenated and/oroxypropylenated) fatty acid esters; oxyalkylenated (oxyethylenatedand/or oxypropylenated) fatty alcohol ethers; sugar esters such assucrose stearate; and mixtures thereof.

The fatty acid esters of a sugar that can be used as nonionicamphiphilic lipids can be chosen in particular from the group comprisingesters or mixtures of esters of a C₈-C₂₂ fatty acid and of sucrose, ofmaltose, of glucose or of fructose, and esters or mixtures of esters ofa C₁₄-C₂₂ fatty acid and of methylglucose. The C₈-C₂₂ or C₁₄-C₂₂ fattyacids forming the fatty unit of the esters that can be used in theemulsion comprise a saturated or unsaturated linear alkyl chain having,respectively, from 8 to 22 or from 14 to 22 carbon atoms. The fatty unitof the esters can be chosen in particular from stearates, behenates,arachidonates, palmitates, myristates, laurates, caprates and mixturesthereof.

By way of example of esters or of mixtures of esters of a fatty acid andof sucrose, of maltose, of glucose or of fructose, mention may be madeof sucrose monostearte, sucrose distearate, sucrose tristearate andmixtures thereof, such as the products sold by the company Croda underthe name Crodesta F50, F70, F110 and F160 having, respectively, an HLB(Hydrophilic Lipophilic Balance) of 5, 7, 11 and 16; and, by way ofexample of esters or of mixtures of esters of a fatty acid and ofmethylglucose, mention may be made of the disearate of methylglucose andof polyglycerol-3, sold by the company Goldschmidt under the nameTego-care 450. Mention may also be made of glucose monoesters or maltosemonoesters, such as methyl O-hexadecanoyl-6-D-glucoside andO-hexadecanoyl-6-D-maltoside.

The fatty alcohol ethers of a sugar that can be used as nonionicamphiphilic lipids can be chosen in particular form the group comprisingethers or mixtures of ethers of a C₈-C₂₂ fatty alcohol and of glucose,of maltose, of sucrose or of fructose, and ethers or mixtures of ethersof a C₁₄-C₂₂ fatty alcohol and of methylglucose. They are in particularalkylpolyglucosides.

The C₈-C₂₂ or C₁₄-C₂₂ fatty alcohols forming the fatty unit of theethers that can be used in the emulsion of the present disclosurecomprise a saturated or unsaturated linear alkyl chain having,respectively, from 8 to 22 or from 14 to 22 carbon atoms. The fatty unitof the ethers can be chosen in particular from decyl, cetyl, behenyl,arachidyl, stearyl, palmityl, myristyl, lauryl, capryl and hexadecanoylunits, and mixtures thereof such as cetearyl.

By way of example of fatty alcohol ethers of a sugar, mention may bemade of alkylpolyglucosides, such as decylglucoside and laurylglucosidesold, for example, by the company Henkel under the respective namesPlantaren 2000 and Plantaren 1200, cetostearylglucoside, optionally as amixture with cetostearyl alcohol, sold, for example, under the nameMontanov 68 by the company Seppic, under the name Tego-care CG90 by thecompany Goldschmidt and under the name Emulgade KE3302 by the companyHenkel, and also arachidylglucoside, for example in the form of themixture of arachidyl and behenyl alcohols and of arachidylglucoside soldunder the name Montanov 202 by the company Seppic.

Use is more particularly made, as nonionic amphiphilic lipid of thistype, of sucrose monostearate, sucrose distearate, sucrose tristearateand mixtures thereof, the distearate of methylglucose and ofpolyglycerol-3, and alkylpolyglucosides.

The glycerol fatty esters that can be used as nonionic amphiphiliclipids can be chosen in particular from the group comprising the estersformed from at least one acid comprising a saturated linear alkyl chainhaving from 16 to 22 carbon atoms, and from 1 to 10 glycerol units. Usemay be made of one or more of these glycerol fatty esters in theemulsion of the instant disclosure.

These esters may be chosen in particular from stearates, behenates,arachidates, palmitates and mixtures thereof. Stearates and palmitatesare preferably used.

By way of example of a surfactant that can be used in the emulsion ofthe instant disclosure, mention may be made of decaglycerolmonostearate, distearate, tristearate and pentastearate (10 glycerolunits) (CTFA names: polyglyceryl-10 stearate, polyglyceryl-10distearate, polyglyceryl-10 tristearate, polyglyceryl-10 pentastearate),such as the products sold under the respective names Nikkol Decaglyn1-S, 2-S, 3-S and 5-S by the company Nikko, and diglyceryl monostearate(CTFA name: polyglyceryl-2 stearate) such as the product sold by thecompany Nikko under the name Nikkol DGMS.

The sorbitan fatty esters that can be used as nonionic amphiphiliclipids chosen in particular from the group comprising esters of aC₁₆-C₂₂ fatty acid and of sorbitan and oxyethylenated esters of aC₁₆-C₂₂ fatty acid and of sorbitan. They are formed from at least onefatty acid comprising at least one saturated linear alkyl chain, having,respectively, from 16 to 22 carbon atoms, and from sorbitol or fromethoxylated sorbitol. The oxyethylenated esters generally comprise from1 to 100 ethylene oxide units, and preferably from 2 to 40 ethyleneoxide (EO) units.

These esters can be chosen in particular from stearates, behenates,arachidates, palmitates and mixtures thereof. Stearates and palmitatesare preferably used.

By way of example of sorbitan fatty ester and of an oxyethylenatedsorbitan fatty ester, mention may be made of sorbitan monostearate (CTFAname: sorbitan stearate) sold by the company ICI under the name Span 60,sorbitan monopalmitate (CTFA name: sorbitan palmitate) sold by thecompany ICI under the name Span 40, or sorbitan 20 EO tristearate (CTFAname: polysorbate 65) sold by the company ICI under the name Tween 65.

The ethoxylated fatty ethers are typically ethers made up of 1 to 100ethylene oxide units and of at least one fatty alcohol chain having from16 to 22 carbon atoms. The fatty chain of the ethers can be chosen inparticular from behenyl, arachidyl, stearyl and cetyl units, andmixtures thereof, such as cetearyl. By way of example of ethoxylatedfatty ethers, mention may be made of ethers of behenyl alcoholcomprising 5, 10, 20 and 30 ethylene oxide units (CTFA names:beheneth-5, beheneth-10, beheneth-20 and beheneth-30), such as theproducts sold under the names Nikkol BBS, BB10, BB20 and BB30 by thecompany Nikko, and the ether of stearyl alcohol comprising 2 ethyleneoxide units (CTFA name: steareth-2), such as the product sold under thename Brij 72 by the company ICI.

The ethoxylated fatty esters that can be used as nonionic amphiphiliclipids are esters made up of 1 to 100 ethylene oxide units and of atleast one fatty acid chain comprising from 16 to 22 carbon atoms. Thefatty chain of the esters can be chosen in particular from stearate,behenate, arachidate and palmitate units, and mixtures thereof. By wayof example of ethoxylated fatty esters, mention may be made of the esterof stearic acid comprising 40 ethylene oxide units, such as the productsold under the name Myrj 52 (CTFA name: PEG-40 stearate) by the companyICI, and the ester of behenic acid comprising 8 ethylene oxide units(CTFA name: PEG-8 behenate), such as the product sold under the nameCompritol HD5 ATO by the company Gattefosse.

The block copolymers of ethylene oxide and of propylene oxide that canbe used as nonionic amphiphilic can be chosen in particular frompoloxamers and in particular from Poloxamer 231, such as the productsold by the company ICI under the name Pluronic L81 of formula (V) withx=z=6, y=39 (HLB 2); Poloxamer 282, such as the product sold by thecompany ICI under the name Pluronic L92 of formula (V) with x=z=10, y=47(HLB 6); and Poloxamer 124, such as the product sold by the company ICIunder the name Pluronic L44 of formula (V) with x=z=11, y=21 (HLB 16).

As nonionic amphiphilic lipids, mention may also be made of the mixturesof nonionic surfactants described in document EP-A-705593, incorporatedherein for reference.

Suitable hydrophobically-modified emulsifiers include, for example,inulin lauryl carbamate, commercially available from Beneo Orafti underthe tradename Inutec SP1.

The above lists are only examples and not limiting.

The total amount of emulsifier present in the compositions is typicallyin an amount of about 0.1, 0.2, or 0.5 wt. % to about 4.0, 5.0, 6.0, or7.5 wt. %, based on the total weight of the composition.

Gelling Agent

Gelling agents may also be included in the sunscreen compositions.

Examples of suitable hydrophilic gelling agents include carboxyvinylpolymers such as the Carbopol products (carbomers) and the Pemulenproducts (acrylate/C10-C30-alkylacrylate copolymer); polyacrylamides,for instance the crosslinked copolymers sold under the names Sepigel 305(CTFA name: polyacrylamide/C13-14 isoparaffin/Laureth 7) or Simulgel 600(CTFA name: acrylamide/sodium acryloyldimethyltauratecopolymerfisohexadecane/polysorbate 80) by the company SEPPIC;2-acrylamido-2-methylpropanesulfonic acid polymers and copolymers, whichare optionally crosslinked and/or neutralized, for instance thepoly(2-acrylamido-2-methylpropanesulfonic acid) sold by the companyHoechst under the trade name “Hostacerin AMPS” (CTFA name: ammoniumpolyacryldimethyltauramide); cellulose-based derivatives such ashydroxyethylcellulose; polysaccharides and especially gums such asxanthan gum; and mixtures thereof.

Lipophilic gelling agents (thickeners) that may be mentioned includemodified clays such as hectorite and its derivatives, for instance theproducts sold under the name bentone.

In some instances, the gelling agent is ammoniumacryloyldimethyltaurate/steareth-25 methacrylate crosspolymer,commercially available from Clariant under the tradename Aristoflex HMS.

The above lists are only examples and not limiting.

The gelling agent is typically used in an amount of about 0.05 to about1.5% by weight, from about 0.08 to about 1.0% by weight, or about 0.1 toabout 0.5% by weight, based on the total weight of the composition.

Additional Sunscreen Filters (Protective Agents)

The sunscreen compositions can include additional sunscreen filters suchas, for example, mineral UV filters. Examples of mineral UV filtersinclude pigments and nanopigments (mean size of the primary particles isgenerally is from 5 nm to 100 nm or from 10 nm to 50 nm) of treated oruntreated metal oxides such as, for example, nanopigments of titaniumoxide (amorphous or crystallized in rutile and/or anatase form), of ironoxide, of zinc oxide, of zirconium oxide or of cerium oxide. The treatednanopigments are pigments that have undergone one or more surfacetreatments of chemical, electronic, mechanochemical and/or mechanicalnature with compounds as described, for example, in Cosmetics &Toiletries, February 1990, Vol. 105, pp. 53-64, such as amino acids,beeswax, fatty acids, fatty alcohols, anionic surfactants, lecithins,sodium, potassium, zinc, iron or aluminium salts of fatty acids, metal(titanium or aluminium) alkoxides, polyethylene, silicones, proteins(collagen or elastin), alkanolamines, silicon oxides, metal oxides,sodium hexametaphosphate, alumina or glycerol. The treated nanopigmentsmay more particularly be titanium oxides treated with:

-   -   silica and alumina, such as the products “Microtitanium Dioxide        MT 500 SA” and “Microtitanium Dioxide MT 100 SA” from the        company Tayca, and the products “Tioveil Fin”, “Tioveil OP”,        “Tioveil MOTG” and “Tioveil IPM” from the company Tioxide;    -   alumina and aluminium stearate, such as the product        “Microtitanium Dioxide MT 100 T” from the company Tayca;    -   alumina and aluminium laurate, such as the product        “Microtitanium Dioxide MT 100 S” from the company Tayca;    -   iron oxides and iron stearate, such as the product        “Microtitanium Dioxide MT 100 F” from the company Tayca;    -   silica, alumina and silicone, such as the products        “Microtitanium Dioxide MT 100 SAS”, “Microtitanium Dioxide MT        600 SAS” and “Microtitanium Dioxide MT 500 SAS” from the company        Tayca;    -   sodium hexametaphosphate, such as the product “Microtitanium        Dioxide MT 150 W” from the company Tayca;    -   octyltrimethoxysilane, such as the product “1-805” from the        company Degussa;    -   alumina and stearic acid, such as the product “UVT-M160” from        the company Kemira;    -   alumina and glycerol, such as the product “UVT-M212” from the        company Kemira;    -   alumina and silicone, such as the product “UVT-M262” from the        company Kemira.

Other titanium oxide nanopigments treated with a silicone are TiO₂treated with octyltrimethylsilane and for which the mean size of theelementary particles is between 25 and 40 nm, such as the product soldunder the trade name “1805” by the company Degussa Silices, TiO₂ treatedwith a polydimethylsiloxane and for which the mean size of theelementary particles is 21 nm, such as the product sold under the tradename “70250 Cardre UF TiO2SI3” by the company Cardre, anatase/rutileTiO₂ treated with a polydimethylhydrogenosiloxane and for which the meansize of the elementary particles is 25 nm, such as the product soldunder the trade name “Microtitanium Dioxide USP Grade Hydrophobic” bythe company Color Techniques.

Uncoated titanium oxide nanopigments are sold, for example, by thecompany Tayca under the trade names “Microtitanium Dioxide MT 500 B” or“Microtitanium Dioxide MT 600 B”, by the company Degussa under the name“P 25”, by the company Wackher under the name “Oxyde de titanetransparent PW”, by the company Myoshi Kasei under the name “UFTR”, bythe company Tomen under the name “ITS” and by the company Tioxide underthe name “Tioveil AQ”.

The uncoated zinc oxide nanopigments are, for example:

-   -   those sold under the name “Z-Cote” by the company Sunsmart;    -   those sold under the name “Nanox” by the company Elementis; and    -   those sold under the name “Nanogard WCD 2025” by the company        Nanophase Technologies.

The coated zinc oxide nanopigments are, for example:

-   -   those sold under the name “Zinc Oxide CS-5” by the company        Toshibi (ZnO coated with polymethylhydrogenosiloxane);    -   those sold under the name “Nanogard Zinc Oxide FN” by the        company Nanophase Technologies (as a 40% dispersion in Finsolv        TN, C₁₂-C₁₅ alkyl benzoate);    -   those sold under the name “Daitopersion ZN-30” and “Daitopersion        ZN-50” by the company Daito (dispersions in        cyclopolymethylsiloxane/oxyethylenated polydimethylsiloxane,        containing 30% or 50% of nanozinc oxides coated with silica and        polymethylhydrogenosiloxane);    -   those sold under the name “NFD Ultrafine ZNO” by the company        Daikin (ZnO coated with perfluoroalkyl phosphate and copolymer        based on pertluoroalkylethyl as a dispersion in        cyclopentasiloxane);    -   those sold under the name “SPD-Z1” by the company Shin-Etsu (ZnO        coated with silicone-grafted acrylic polymer, dispersed in        cyclodimethylsiloxane);    -   those sold under the name “Escalol Z100” by the company ISP        (alumina-treated ZnO dispersed in an ethylhexyl        methoxycinnamate/PVP-hexadecene/methicone copolymer mixture);    -   those sold under the name “Fuji ZNO-SMS-10” by the company Fuji        Pigment (ZnO coated with silica and polymethylsilsesquioxane);        and    -   those sold under the name “Nanox Gel TN” by the company        Elementis (ZnO dispersed at a concentration of 55% in C₁₂-C₁₅        alkyl benzoate with hydroxystearic acid polycondensate).

The uncoated cerium oxide nanopigments are sold under the name“Colloidal Cerium Oxide” by the company Rhone-Poulenc. The uncoated ironoxide nanopigments are sold, for example, by the company Arnaud underthe names “Nanogard WCD 2002 (FE 45B)”, “Nanogard Iron FE 45 BL AQ”,“Nanogard FE 45R AQ” and “Nanogard WCD 2006 (FE 45R)” or by the companyMitsubishi under the name “TY-220”. The coated iron oxide nanopigmentsare sold, for example, by the company Arnaud under the names “NanogardWCD 2008 (FE 45B FN)”, “Nanogard WCD 2009 (FE 45B 556)”, “Nanogard FE 45BL 345” and “Nanogard FE 45 BL” or by the company BASF under the name“Transparent Iron Oxide”.

Mixtures of metal oxides may also be used, especially of titaniumdioxide and of cerium dioxide, including the silica-coated equal-weightmixture of titanium dioxide and of cerium dioxide, sold by the companyIkeda under the name “Sunveil A”, and also the alumina, silica andsilicone-coated mixture of titanium dioxide and of zinc dioxide, such asthe product “M 261” sold by the company Kemira, or the alumina, silicaand glycerol-coated mixture of titanium dioxide and of zinc dioxide,such as the product “M 211” sold by the company Kemira.

The above lists are only examples and not limiting.

The compositions according to the instant disclosure may be preparedaccording to techniques that are well known to those skilled in the art,in particular those intended for the preparation of emulsions ofoil-in-water or water-in-oil type. They may be in particular in the formof a simple or complex emulsion (O/W, W/O, O/W/O or W/O/W emulsion) suchas a cream or a milk, in the form of a gel or a cream-gel, or in theform of a lotion.

The instant disclosure will be better understood from the examples thatfollow, all of which are intended for illustrative purposes only and arenot meant to limit the scope of the instant disclosure in any way.

Examples 1-11

Samples comprising different amounts of UV filters were prepared bydissolving the UV filters in ethanol and solvent as illustrated in thetable below.

TABLE 1 Ingredient Range Octocrylene 2-7% Avobenzone 1-3% Octisalate1-5% Homosalate  2-10% Eldew SL205 Solvent*  5% Dermacryl 79** 10%Ethanol Qs 100% *Eldew SL 205 (Ajinomoto) is Isopropyl LauroylSarcosinate (emollient) **Dermacryl 79 (Akzo Nobel) is anacrylate/octylacrylamide Copolymner (film-former)

Each sample was applied to a PPMA plate with a draw down bar to controlthe thickness and the homogeneity of the film. The in vitro SPF wasmeasured using a Labsphere 2000. Each measurement was made 6 times (6times on each plate) on 3 plates for each composition. The amount of UVfilters included in each sample and the resulting SPF is reported in thetable below.

TABLE 2 Total UV No. Octocrylene Avobenzone Oxybenzone OctisalateHomosalate Filters SPF 1 5.92 2.96 0.04 4.88 8.78 22.58 92.73Comparisons 2 4.80 2.40 0.60 2.20 7.60 17.60 19.82 3 2.80 1.40 0.60 3.008.40 16.20 15.27 4 5.20 2.60 0.60 2.80 7.60 18.80 44.54 5 3.60 1.80 1.804.60 7.60 19.40 23.81 6 5.20 2.60 1.80 4.20 6.00 19.80 33.86 7 2.40 1.201.80 4.60 10.00 20.00 25.13 8 5.60 2.80 1.80 2.60 10.00 22.80 68.81 95.60 2.80 1.20 5.00 10.00 24.60 66.05 10 4.00 2.00 1.20 2.80 8.40 18.4031.19 11 5.20 2.60 1.20 1.80 7.60 18.40 29.73

The following table corresponds to the table above but lists each UVfilter as a ratio relative to avobenzone.

TABLE 3 Ratio (Octocylene:Avobenzone: Oxybenzone:Octisalate:Homosalate)Total UV No. Relative to Avobenzone Filters SPF 12.00:1.00:0.01:1.65:2.97 22.58 92.73 2 2.00:1.00:0.25:0.92:3.17 17.6019.82 3 2.00:1.00:0.43:2.14:6.00 16.20 15.27 4 2.00:1.00:0.23:1.08:2.9218.80 44.54 5 2.00:1.00:1.00:2.56:4.22 19.40 23.81 62.00:1.00:0.69:1.62:2.31 19.80 33.86 7 2.00:1.00:1.50:3.83:8.33 20.0025.13 8 2.00:1.00:0.64:0.93:3.57 22.80 68.81 9 2.00:1.00:0.43:1.79:3.5724.60 66.05 10 2.00:1.00:0.60:1.40:4.20 18.40 31.19 112.00:1.00:0.46:0.69:2.92 18.40 29.73 *Note: the bolded numbers falloutside the claimed range.

As illustrated in the tables above, Example 1 having ratio of about2.0:1.00:0.01:1.65:2.97 (Octocylene:Avobenzone:Oxybenzone:Octisalate)shows an dramatic jump in SPF.

Example 12

Using the procedures described above for Examples 1-12, the followingcomposition was prepared and the SPF measured.

TABLE 4 Clear Spray-On Sunscreen SPF UVB 172 Ingredient AmountOctocrylene 5.92 Avobenzone 2.96 Oxybenzone 0.04 Octisalate 4.88Homosalate 8.78 Eldew SL205 Solvent* 5 Dermacryl 79** 10 Ethanol q.s.100 *Eldew SL 205 (Ajinomoto) is Isopropyl Lauroyl Sarcosinate(emollient) **Dermacryl 79 (Akzo Nobel) is an acrylate/octylacrylamideCopolymner (film-former)

Example 13

Suncscreen FORMULA: 888513 total %: 100.000 Phase Substituent % wt/wtA-1 Water 31.52 O/W emulsifier 0.1 to 2.0 A-2 Water Q.S. Disodium EDTA0.100 Preservative 0.1 to 0.7 A-3 O/W emulsifier 0.1 to 2.0 B Avobenzone2.96 Octocrylene 5.92 Benzophenone-3 0.04 Octyl Salicylate 4.88Homosalate 8.78 Emollient 2.0 to 7.0 W/O emulsifier 0.1 to 2.5 CoEmulsifier 0.1 to 2.0 Preservative 0.1 to 1.0 Silicone 1.0 to 3.0 CSilicone 01.0 to 4.0  D Tocopherol 0.100 D Wetting agent 0.1 to 1.5

1. A sunscreen composition comprising the following combination of UVfilters: octocrylene, avobenzone, octisalate, and homosalate, andoptionally oxybenzone; wherein the ratio of each filter relative toavobenzone is as follows: the ratio of octocrylene to avobenzone is1.6:1.0 to 2.4:1.0, the ratio of oxybenzone to avobenzone 0.0:1.0 to0.016:1.0, the ratio of octisalate to avobenzone is 1.3:1.0 to 2.0:1.0,and the ratio of homosalate to avobenzone is 2.3:1.0 to 3.6:1.
 2. Thesunscreen composition according to claim 1, wherein the ratio of eachfilter relative to avobenzone is about: 2.0:1.0:0.0:1.7:3.0(octocrylene:avobenzone:oxybenzone:octisalate:homosalate).
 3. Thesunscreen composition according to claim 1 having an SPF of at least 15.4. The sunscreen composition according to claim 1 having an SPF of atleast
 30. 5. The sunscreen composition according to claim 1 having anSPF of at least
 50. 6. The sunscreen composition according to claim 1having an SPF of at least
 75. 7. The sunscreen composition according toclaim 1 having an SPF of at least
 100. 8. The sunscreen compositionaccording to claim 1, wherein the sunscreen composition comprises lessthan 0.5% oxybenzone.
 9. The sunscreen composition according to claim 1comprising: about 5.9 wt. % octocrylene; about 3.0 wt. % avobenzone;about 4.9 wt. % octisalate; and about 8.8 wt. % homosalate.
 10. Thesunscreen composition according to claim 1 further comprising a booster.11. A method of protecting a keratinous substrate from ultravioletradiation comprising applying a sunscreen composition according to claim1 to the keratinous substrate.
 12. A method of absorbing ultravioletlight comprising applying a sunscreen composition according to claim 1to a keratinous substrate and subjecting the keratinous substrate toultraviolet light.